JPH025740B2 - - Google Patents
Info
- Publication number
- JPH025740B2 JPH025740B2 JP58022171A JP2217183A JPH025740B2 JP H025740 B2 JPH025740 B2 JP H025740B2 JP 58022171 A JP58022171 A JP 58022171A JP 2217183 A JP2217183 A JP 2217183A JP H025740 B2 JPH025740 B2 JP H025740B2
- Authority
- JP
- Japan
- Prior art keywords
- item
- alcohol
- synthesis method
- reaction
- carbon monoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000006243 chemical reaction Methods 0.000 claims description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 15
- RENMDAKOXSCIGH-UHFFFAOYSA-N Chloroacetonitrile Chemical group ClCC#N RENMDAKOXSCIGH-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 150000007960 acetonitrile Chemical class 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000001308 synthesis method Methods 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- -1 alkaline earth metal carbonate Chemical class 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- REXUYBKPWIPONM-UHFFFAOYSA-N 2-bromoacetonitrile Chemical compound BrCC#N REXUYBKPWIPONM-UHFFFAOYSA-N 0.000 claims description 2
- VODKOOOHHCAWFR-UHFFFAOYSA-N 2-iodoacetonitrile Chemical compound ICC#N VODKOOOHHCAWFR-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- MQIKJSYMMJWAMP-UHFFFAOYSA-N dicobalt octacarbonyl Chemical group [Co+2].[Co+2].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] MQIKJSYMMJWAMP-UHFFFAOYSA-N 0.000 claims description 2
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims 3
- 235000019441 ethanol Nutrition 0.000 claims 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229940035429 isobutyl alcohol Drugs 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- ANGDWNBGPBMQHW-UHFFFAOYSA-N methyl cyanoacetate Chemical compound COC(=O)CC#N ANGDWNBGPBMQHW-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- MLIREBYILWEBDM-UHFFFAOYSA-M 2-cyanoacetate Chemical compound [O-]C(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- UMYVESYOFCWRIW-UHFFFAOYSA-N cobalt;methanone Chemical compound O=C=[Co] UMYVESYOFCWRIW-UHFFFAOYSA-N 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- JAUCIKCNYHCSIR-UHFFFAOYSA-M sodium;2-cyanoacetate Chemical compound [Na+].[O-]C(=O)CC#N JAUCIKCNYHCSIR-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明はシアノ酢酸エステルの合成方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for synthesizing cyanoacetic esters.
シアノ酢酸エステルは有機合成中間体などに用
いられる物質である。従来採用されて来た合成方
法は、例えばOrganic Synthesis Collect
Volum1の254頁によれば以下の通りである。 Cyanoacetate is a substance used as an intermediate in organic synthesis. Conventional synthesis methods include Organic Synthesis Collect, for example.
According to page 254 of Volume 1, it is as follows.
まずモノクロル酢酸水溶液に炭酸ナトリウムを
加えて中和し、モノクロル酢酸ナトリウム水溶液
とする。これにシアン化ナトリウム水溶液を加え
てシアノ酢酸ナトリウムを合成する。反応液に濃
塩酸を加えてシアノ酢酸を遊離させた後に、減圧
蒸留にて溶媒を除去し、釜残にアルコールを加え
て硫酸触媒下にエステル化する。炭酸ナトリウム
で硫酸を中和後、油層および水相のエーテル抽出
液を減圧蒸留すると純度97〜98％のシアノ酢酸エ
ステルが収率77〜80％で得られる。 First, sodium carbonate is added to a monochloroacetic acid aqueous solution to neutralize it to obtain a monochloroacetic acid aqueous solution. A sodium cyanide aqueous solution is added to this to synthesize sodium cyanoacetate. After adding concentrated hydrochloric acid to the reaction solution to liberate cyanoacetic acid, the solvent is removed by distillation under reduced pressure, alcohol is added to the residue, and esterification is carried out under a sulfuric acid catalyst. After neutralizing the sulfuric acid with sodium carbonate, the ether extracts of the oil and aqueous phases are distilled under reduced pressure to obtain cyanoacetate with a purity of 97-98% and a yield of 77-80%.
しかしながらこの方法は毒性の強い青酸ソーダ
や、腐食性の強い酸触媒を用いるうえに、反応工
程も多く、収率も80％以下であるという欠点があ
る。 However, this method has the drawbacks of using highly toxic sodium cyanide and highly corrosive acid catalysts, requiring many reaction steps, and yielding less than 80%.
本発明の目的は、このような欠点のない低温度
でしかも一段階でシアノ酢酸エステルを高収率で
得る合成方法を提供することである。 The object of the present invention is to provide a synthetic method that does not have such drawbacks and can obtain cyanoacetic esters in high yields at low temperatures and in one step.
本願発明者等はこの目的を達成するため鋭意研
究の結果、本発明のモノハロゲン化アセトニトリ
ル、低級アルコールおよび一酸化炭素を塩基物質
および触媒の存在において反応させることから成
るシアノ酢酸エステルの合成方法に到達した。 In order to achieve this objective, the inventors of the present application have conducted extensive research and have developed a method for synthesizing cyanoacetic esters of the present invention, which comprises reacting monohalogenated acetonitrile, lower alcohol, and carbon monoxide in the presence of a basic substance and a catalyst. Reached.
すなわち、本発明の方法は、
Ｘ−CH2−ON＋CO＋ROH〓〓〓〓NC−
CH2COOR
なる反応を利用せんとするものである。（式中、
Ｘはハロゲン原子、Ｒはアルキル基を示す）
本発明において原料として使用されるモノハロ
ゲン化アセトニトリルはクロロアセトニトリル、
ブロモアセトニトリル、ヨードアセトニトリルで
ある。 That is, the method of the present invention is as follows:
It attempts to utilize the reaction CH 2 COOR. (In the formula,
(X is a halogen atom, R is an alkyl group) The monohalogenated acetonitrile used as a raw material in the present invention is chloroacetonitrile,
Bromoacetonitrile and iodoacetonitrile.
アルコールとしてはメチル、エチル、プロピ
ル、イソプロピルブチル、sec−ブチル、tert−
ブチルアルコール等の低級アルコールが使用され
る。 Alcohols include methyl, ethyl, propyl, isopropyl butyl, sec-butyl, tert-
Lower alcohols such as butyl alcohol are used.
一酸化炭素は純粋なものが好ましいが、不活性
な希ガス類や、小量の水素を含むものでも使用す
ることが出来る。一酸化炭素の分圧は１〜100気
圧である。１気圧未満でもよいが、反応速度の面
から不利であり、100気圧超では経済的に不利で
ある。 Although carbon monoxide is preferably pure, inert rare gases or those containing a small amount of hydrogen can also be used. The partial pressure of carbon monoxide is between 1 and 100 atmospheres. Although it may be less than 1 atmosphere, it is disadvantageous in terms of reaction rate, and if it exceeds 100 atmospheres, it is economically disadvantageous.
塩基物質としては、反応において生成するハロ
ゲン化水素のアクセプターとして、アルカリ金属
及びアルカリ土類金属の炭酸塩、重炭酸塩、酢酸
塩、塩化物、水酸化物、アルコラートなどの無機
塩基、並びにトリエチルアミン等の第３級アミン
や置換ピリジンなどの有機塩基が使用される。特
に、炭酸ナトリウム、炭酸カリウム、トリエチル
アミン、ルチジン等の使用が好ましい。 Examples of basic substances include inorganic bases such as alkali metal and alkaline earth metal carbonates, bicarbonates, acetates, chlorides, hydroxides, and alcoholates, as well as triethylamine, as acceptors for hydrogen halides produced in the reaction. Organic bases such as tertiary amines and substituted pyridines are used. Particularly preferred are sodium carbonate, potassium carbonate, triethylamine, lutidine, and the like.
塩基物質の使用量は、原料のモノハロゲン化ア
セトニトリルと等モルのハロゲン化水素と反応し
て、ハロゲン化物を生成するのに必要な理論値の
１／２以上が使用される。 The amount of the basic substance used is 1/2 or more of the theoretical value required to generate a halide by reacting with monohalogenated acetonitrile as a raw material and equimolar hydrogen halide.
触媒としては、コバルトテトラカルボニルアニ
オンCo（CO）4 -を生じるものであれば何でもよい
が、ジコバルトオクタカルボニルが好適に使用さ
れる。ヒドロコバルトテトラカルボニル及びその
ナトリウム塩及びコバルトテトラカルボニルアニ
オン溶液等も使用できる。 Any catalyst may be used as long as it produces cobalt tetracarbonyl anion Co(CO) 4 - , but dicobalt octacarbonyl is preferably used. Hydrocobalt tetracarbonyl and its sodium salt, cobalt tetracarbonyl anion solutions, etc. can also be used.
触媒の量はハロゲン化アセトニトリル１モルに
対して、1/1000〜1/2モル、好ましくは1/100〜1/
５モルが使用される。1/1000モル未満でもよいが、
反応速度の面から不利であり、1/2モル超では経
済的に不利である。 The amount of catalyst is 1/1000 to 1/2 mol, preferably 1/100 to 1/2 mol, per 1 mol of halogenated acetonitrile.
5 moles are used. It may be less than 1/1000 mole, but
This is disadvantageous in terms of reaction rate, and if it exceeds 1/2 mole, it is economically disadvantageous.
溶媒は、特になくとも反応は進行するが、炭化
水素類、エーテル、ケトン、エステル等の有機溶
媒を使用する事が出来る。 Although the reaction proceeds without any particular solvent, organic solvents such as hydrocarbons, ethers, ketones, and esters can be used.
また、無機塩基を用いる場合には、適量の水の
添加が反応速度を向上せしめる。 Furthermore, when an inorganic base is used, addition of an appropriate amount of water improves the reaction rate.
反応温度は10゜〜150℃、好ましくは30〜70℃で
ある。 The reaction temperature is 10° to 150°C, preferably 30 to 70°C.
反応後、オートクレーブを冷却して反応液を取
り出し、既知の方法で触媒、塩基を除去した後、
常圧もしくは減圧蒸留によつてシアノ酢酸エステ
ルを得る事が出来る。 After the reaction, the autoclave is cooled, the reaction solution is taken out, and the catalyst and base are removed using a known method.
Cyanoacetic acid ester can be obtained by distillation under normal pressure or reduced pressure.
次に、本発明の実施例を示すが、本発明の要旨
を越えない限り、以下の実施例に限定されるもの
ではない。 Next, examples of the present invention will be shown, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.
〈実施例 １〉
200CCステンレス製オートクレーブにクロルア
セトニトリル４ml（64mmol）、メタノール40ml、
水0.5ml、Na2CO34ｇ（38mmol）、Co2（CO）81.2
ｇを仕込み気相を一酸化炭素でパージ後、20Kg／
cm2まで一酸化炭素を圧入した。55℃で４時間反応
を行なつたところ、クロルアセトニトリルの転化
率100％、シアノ酢酸メチルの収率93％（原料ク
ロルアセトニトリル基準）であつた。<Example 1> In a 200CC stainless steel autoclave, 4 ml (64 mmol) of chloracetonitrile, 40 ml of methanol,
0.5 ml of water, 4 g of Na 2 CO 3 (38 mmol), 1.2 of Co 2 (CO) 8
After charging 20kg/g and purging the gas phase with carbon monoxide, 20kg/
Carbon monoxide was injected up to cm2 . When the reaction was carried out at 55° C. for 4 hours, the conversion of chloroacetonitrile was 100% and the yield of methyl cyanoacetate was 93% (based on the raw material chloroacetonitrile).
〈実施例 ２〉
200CCステンレス製オートクレーブにクロルア
セトニトリル４ml（64mmol）、メタノール20ml、
トルエン20ml、トリエチルアミン８ml
（57mmol）、Co2（CO）81.2ｇを仕込み気相を一酸
化炭素でパージ後、20Kg／cm2まで一酸化炭素を圧
入した。55℃で４時間反応を行なつたところ、ク
ロルアセトニトリルの転化率100％、シアノ酢酸
メチルの収率91％であつた。<Example 2> In a 200CC stainless steel autoclave, 4 ml (64 mmol) of chloracetonitrile, 20 ml of methanol,
20ml toluene, 8ml triethylamine
(57 mmol) and 1.2 g of Co 2 (CO) 8 were charged, and after purging the gas phase with carbon monoxide, carbon monoxide was pressurized to 20 Kg/cm 2 . When the reaction was carried out at 55°C for 4 hours, the conversion of chloroacetonitrile was 100% and the yield of methyl cyanoacetate was 91%.
〈実施例 ３〉
200CCステンレス製オートクレーブにクロルア
セトニトリル５ml（80mmol）、エタノール20ml、
トルエン20ml、2.6ルチジン10ml（86mmol）、
Co2（CO）81.2ｇを仕込み気相を一酸化炭素のパー
ジ後、30Kg／cm2まで一酸化炭素を圧入した。55℃
で４時間反応を行なつたところ、クロルアセトニ
トリルの転化率97％、シアノ酢酸エチルの収率96
％であつた。<Example 3> In a 200CC stainless steel autoclave, 5 ml (80 mmol) of chloracetonitrile, 20 ml of ethanol,
20 ml of toluene, 10 ml (86 mmol) of 2.6 lutidine,
After 1.2 g of Co 2 (CO) 8 was charged and the gas phase was purged of carbon monoxide, carbon monoxide was pressurized to 30 kg/cm 2 . 55℃
When the reaction was carried out for 4 hours, the conversion rate of chloroacetonitrile was 97%, and the yield of ethyl cyanoacetate was 96%.
It was %.
〈実施例 ４〉
200CCステンレス製オートクレーブにクロルア
セトニトリル５ml（80mmol）、メタノール20ml、
トルエン20ml、2.6ルチジン10ml（86mmol）、
Co2（CO）81.2ｇを仕込み気相を一酸化炭素でパー
ジ後、30Kg／cm2まで一酸化炭素を圧入した。55℃
で３時間反応を行なつたところ、クロルアセトニ
トリルの転化率97％、シアノ酢酸メチルの収率97
％であつた。<Example 4> In a 200CC stainless steel autoclave, 5 ml (80 mmol) of chloracetonitrile, 20 ml of methanol,
20 ml of toluene, 10 ml (86 mmol) of 2.6 lutidine,
After 1.2 g of Co 2 (CO) 8 was charged and the gas phase was purged with carbon monoxide, carbon monoxide was pressurized to 30 kg/cm 2 . 55℃
When the reaction was carried out for 3 hours, the conversion rate of chloroacetonitrile was 97%, and the yield of methyl cyanoacetate was 97%.
It was %.
〈実施例 ５〉
200CCステンレス製オートクレーブにクロルア
セトニトリル２ml（32mmol）、メタノール30ml、
トルエン30ml、2.6ルチジン４ml（34mmol）、
Co2（CO）81.6ｇを仕込み気相を一酸化炭素でパー
ジ後、２Kg／cm2まで一酸化炭素を圧入した。55℃
で９時間反応を行なつたところ、クロルアセトニ
トリルの転化率52％、シアノ酢酸メチルの収率51
％であつた。<Example 5> In a 200CC stainless steel autoclave, 2 ml (32 mmol) of chloroacetonitrile, 30 ml of methanol,
30 ml of toluene, 4 ml (34 mmol) of 2.6 lutidine,
After charging 1.6 g of Co 2 (CO) 8 and purging the gas phase with carbon monoxide, carbon monoxide was pressurized to 2 kg/cm 2 . 55℃
When the reaction was carried out for 9 hours, the conversion rate of chloroacetonitrile was 52%, and the yield of methyl cyanoacetate was 51%.
It was %.
Claims (1)
ール及び一酸化炭素を、塩基物質及びコバルトカ
ルボニル触媒の存在において、反応させることか
ら成るシアノ酢酸エステルの合成方法。 ２ 該モノハロゲン化アセトニトリルは、クロロ
アセトニトリル、ブロモアセトニトリル又はヨー
ドアセトニトリルである第１項の合成方法。 ３ 該低級アルコールは、メチルアルコール、エ
チルアルコール、プロピルアルコール、イソプロ
ピルアルコール、ブチルアルコール、イソブチル
アルコール、sec−ブチルアルコール又はtert−
ブチルアルコールである第１項の合成方法。 ４ 該一酸化炭素の分圧は、１〜100気圧である
第１項の合成方法。 ５ 該塩基物質は、第３級アミンやピリジン、置
換ピリジンなどの有機塩基である第１項の合成方
法。 ６ 該塩基物質は、アルカリ金属又はアルカリ土
類金属の炭酸塩、重炭酸塩、酢酸塩、酸化物、水
酸化物又はアルコラートである第１項の合成方
法。 ７ 該反応は、水を添加して行われる第６項の合
成方法。 ８ 該触媒は、ジコバルトオクタカルボニル、ヒ
ドロコバルトテトラカルボニル又はそのナトリウ
ム塩又はコバルトカルボニルアニオン溶液である
第１項の合成方法。 ９ 該触媒の量は、モノハロゲン化アセトニトリ
ル１モルに対して1/1000〜1/2モルである第１項
の合成方法。 １０ 該反応は、溶媒中で行われる第１項の合成
方法。[Claims] 1. A method for synthesizing a cyanoacetic ester, which comprises reacting monohalogenated acetonitrile, a lower alcohol, and carbon monoxide in the presence of a basic substance and a cobalt carbonyl catalyst. 2. The synthesis method according to item 1, wherein the monohalogenated acetonitrile is chloroacetonitrile, bromoacetonitrile, or iodoacetonitrile. 3 The lower alcohol is methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, sec-butyl alcohol, or tert-butyl alcohol.
The method for synthesizing item 1, which is butyl alcohol. 4. The synthesis method according to item 1, wherein the partial pressure of the carbon monoxide is 1 to 100 atmospheres. 5. The synthesis method according to item 1, wherein the basic substance is an organic base such as a tertiary amine, pyridine, or substituted pyridine. 6. The method of synthesis according to item 1, wherein the basic substance is an alkali metal or alkaline earth metal carbonate, bicarbonate, acetate, oxide, hydroxide, or alcoholate. 7. The synthesis method of item 6, wherein the reaction is carried out by adding water. 8. The synthesis method according to item 1, wherein the catalyst is dicobalt octacarbonyl, hydrocobalt tetracarbonyl, or a sodium salt thereof, or a cobalt carbonyl anion solution. 9. The synthesis method according to item 1, wherein the amount of the catalyst is 1/1000 to 1/2 mol per 1 mol of monohalogenated acetonitrile. 10. The synthetic method of item 1, wherein the reaction is carried out in a solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58022171A JPS59148751A (en) | 1983-02-15 | 1983-02-15 | Synthesis of cyanoacetic ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58022171A JPS59148751A (en) | 1983-02-15 | 1983-02-15 | Synthesis of cyanoacetic ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59148751A JPS59148751A (en) | 1984-08-25 |
| JPH025740B2 true JPH025740B2 (en) | 1990-02-05 |
Family
ID=12075355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58022171A Granted JPS59148751A (en) | 1983-02-15 | 1983-02-15 | Synthesis of cyanoacetic ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59148751A (en) |
-
1983
- 1983-02-15 JP JP58022171A patent/JPS59148751A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59148751A (en) | 1984-08-25 |
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